Textbook-Integrated Guide to Educational Resources

TIGER

Molecular Models of DNAWilliam F. ColemanThe featured molecules this month come from the paper by David T. Crouse on the X-ray determination of the structure of DNA. Given that most students are aware of the double helix, it seems appropriate to back up a little and examine the components that give rise to this structure. Accordingly, the molecule collection includes: Purine and pyrimidine, structural precursors of the four bases found in DNA: cytosine (C), thymine (T), adenine (A), and guanine (G) The four corresponding deoxyribonucleosides The four deoxyribonucleotides (the nucleoside monophosphates) A two-base-pair fragment showing the AT and GC hydrogen-bonded complements Several small 24-base-pair DNA fragments polyAT, polyGC, and a random array of bases. The DNA fragments provide a good opportunity to have students explore features of the Jmol and Chime menus. Using the Jmol menu as an example (right-click on the structure to bring up the menu) students can use the measuring tools to get an idea of the length of a complete turn in the DNA, the relative widths of the major and minor grooves, and the diameter of the helix. They can use the coloring schemes to detect the various base pair combinations, and learn to read the code for the random sequence. In Chime they can use the Shapely coloring scheme for this same purpose. Exploring other aspects of the menu will allow students to present the molecules in the various forms, including ribbon and cartoon views. In RNA, thymine is replaced by uracil, and the sugar moiety has an axial hydroxyl group on the carbon atom adjacent to the base binding site (the 2? carbon). The structures of uracil and of uridine monophosphate are included in the molecule collection. Students can use the Web to download and examine more complex DNAs using a site such as the Nucleic Acid Database at Rutgers University.

Nucleic Acids / DNA / RNA

Molecular Models of DAPIWilliam F. ColemanThis month's Featured Molecule is DAPI (4′,6-diamidino-2-phenylindole), from the paper by Eamonn F. Healy (1). The utility of DAPI is a consequence of its being a minor-groove binder to DNA. A crystal structure of DAPI binding to the minor groove of a synthetic DNA has been determined, and the structure file made available through the RCSB Protein Data Bank (2, 3). That structure is also included in the Featured Molecules Collection, with the water molecules removed for the sake of clarity. For many students this may be their first encounter with the binding of small molecules to DNA. Another example of such binding is the intercalation of the antibiotic actinomycin into DNA. The Department of Biology at the University of Hamburg maintains an excellent Web site showing both crystal and NMR structures of actinomycin intercalation (4). Observant students will also note in the structure of DAPI a theme that has appeared several times in our Featured Molecules, and that is the non-planarity of adjacent delocalized ring systems. In DAPI, it is a five-membered ring adjacent to a six-membered ring, and the observed departure from planarity is less than that in biphenyl. Students might be asked to explain that difference.

Biomolecules (Netorials)Rachel Bain, Mithra Biekmohamadi, Liana Lamont, Mike Miller, Rebecca Ottosen, John Todd, and David ShawBiomolecules: this is a resource in the collection "Netorials". This set of modules will provide you with a descriptive overview of the four major classes of biomolecules found in all living organisms: carbohydrates, lipids, proteins, and nucleic acids. The Netorials cover selected topics in first-year chemistry including: Chemical Reactions, Stoichiometry, Thermodynamics, Intermolecular Forces, Acids & Bases, Biomolecules, and Electrochemistry.

Molecular Models of Products and Reactants from Suzuki and Heck SynthesesWilliam F. ColemanOur Featured Molecules this month come from the paper by Evangelos Aktoudianakis, Elton Chan, Amanda R. Edward, Isabel Jarosz, Vicki Lee, Leo Mui, Sonya S. Thatipamala, and Andrew P. Dicks (1), in which they describe the synthesis of 4-phenylphenol using an aqueous-based Suzuki reaction. The authors describe the various ways in which this reaction addresses concerns of green chemistry, and point out that their product bears structural similarity to two non-steroidal anti-inflammatory drugs (NSAIDs), felbinac and diflunisal. A number of molecules from this paper and its online supplemental material have been added to the Featured Molecules collection. Students will first notice that the aromatic rings in the molecules based on a biphenyl backbone are non-planar, as is the case in biphenyl. If they look carefully at diflunisal, they will notice that the carbon atoms are in a different chemical environment. One way in which to see the effect of these differing environments is to examine the effect of atom charge on the energies of the carbon 1s orbitals. Figure 1 shows this effect using charges and energies from an HF/631-G(d) calculation. A reasonable question to ask students would be to assign each of the data points to the appropriate carbon atom. As an extension of this exercise students could produce similar plots using different computational schemes. Are the results the same; are they parallel. This would be a useful problem when dealing with the tricky question of exactly what is meant by atom charge in electronic structure calculations. Students with more expertise in organic chemistry could explore extending the synthesis of 4-phenylphenol to produce more complex bi- and polyphenyl-based drugs. This may well be the first time that they have seen coupling reactions such as the Suzuki and Heck reactions. Students in introductory and non-science-major courses might well find the NSAIDs to be an interesting group of molecules, and could be asked to find information on the variety of molecules that display the anti-inflammatory properties associated with NSAIDs. Do they find structural similarities? Are there various classes of NSAIDs? Are they familiar with any of these molecules? Have they taken any NSAIDs? If so, for what reason? Is there any controversy about any of the NSAIDs? As with all of the molecules in the Featured Molecules collections, those added this month provide us with a number of ways of showing students the practical relevance of what they sometime see only as lines on a page. Molecules do matter.

Synthesis

Creative ChemistryVolume 04, issue 15 of a series of leaflets covering subjects of interest to students of elementary chemistry distributed in 1929 - 1932.

Applications of Chemistry |

Synthesis

Molecular Models of Plant HormonesWilliam F. ColemanThe paper "Synthesis of Plant Auxin Derivatives and Their Effects on Ceratopteris richardii" by Corey E. Stilts and Roxanne Fisher describing an experiment begun in the organic labs and completed in a biochemistry cell biology lab provides the featured molecules for this month. The molecules in Figure 1 of that paper have been added to the collection. There is nothing particularly surprising about their structures, but students might be interested in seeing whether they can determine any structure/regulating effect relationships as the number of synthesized auxin derivatives grows. Additionally, students with little or no biochemistry background might wish to explore other systems that act as growth regulating hormones in plants, as an introduction to the variety of molecular structures that can display such bioactivity. Such molecules range from the very simple, ethene, to the adenine-derived cytokinins (an example of which, zealtin, is shown here) and the brassinosteroids. Brassinolide, a commonly occurring brassin, is also shown. These latter two structures have also been added to the molecule collection. All of the structures have been optimized at the HF/6-31G(d) level.